Poly[[aqua-μ₆-benzene-1,2,3-tricarboxyl­ato-μ₃-hydroxido-dizinc] hemihydrate]

In the title compound, {[Zn₂(C₉H₃O₆)(OH)(H₂O)]·0.5H₂O}_n, there are three independent Zn^II atoms present; two are located on special positions, viz a twofold rotation axis and an inversion centre, and the third is located in a general position. The Zn^II atom on the inversion centre is six-coordinated by four O atoms from four different benzene-1,2,3-tricarboxyl­ate anions and two OH⁻ anions. The Zn^II atom located on a twofold axis is four coordinated by two O atoms from two different benzene-1,2,3-tricarboxyl­ate anions and two OH⁻ anions. The third Zn^II atom, located in a general position, is five coordinated by three O atoms from three different benzene-1,2,3-tricarboxyl­ate anions, one OH⁻ anion and one water mol­ecule. Each benzene-1,2,3-tricarboxyl­ate anion bridges six Zn^II atoms, and the OH⁻ anion bridges three Zn^II atoms, resulting in the formation of a three-dimensional framework. A series of O—H...O hydrogen bonds involving the benzene-1,2,3-tricarboxyl­ate anions, the OH⁻ anion and the coordinating and the two water solvent mol­ecules further stablize the crystal structure. The two solvent water molecules show occupancies of 0.5 and 0.25.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• Disorder in solvent or counterion
• R factor = 0.035
• wR factor = 0.090
• Data-to-parameter ratio = 10.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor      *O2W    -  *H2WA   ...          ?

Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...        3.1 Ratio
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0078 Ang
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT975_ALERT_2_C Positive Residual Density at 0.62A from O2W    .       0.75 eA-3
PLAT975_ALERT_2_C Positive Residual Density at 0.64A from O2W    .       0.68 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.51A from O1W    .      -0.57 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.51A from O1W    .      -0.45 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.88A from O1W    .      -0.44 eA-3
PLAT976_ALERT_2_C Negative Residual Density at 0.70A from O1W    .      -0.42 eA-3

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C9 H7 O8.5 Zn2
            Atom count from _chemical_formula_moiety:C9 H6 O8.5 Zn2
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         10
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          3
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...          3 Units
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................        100 Perc.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C5     ..  O3W     ..       3.00 Ang.
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            O2  -ZN1 -O2  -C7     12.00  0.00   9.656   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            O1W -ZN3 -O7  -ZN2  -172.00  0.90   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         22
            O1W -ZN3 -O7  -ZN1    60.30  1.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         25
            O7  -ZN1 -O7  -ZN2   118.70  0.50   9.656   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         30
            O7  -ZN1 -O7  -ZN3  -106.60  0.30   9.656   1.555   1.555   1.555
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          5
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.13 Ratio
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2
              H O0.50
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3
              H0.50 O0.25
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          8
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          45 Perc.
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
  11 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  22 ALERT level G = General information/check it is not something unexpected

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  10 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
  10 ALERT type 4 Improvement, methodology, query or suggestion
   4 ALERT type 5 Informative message, check

---

S1. Comment

The title compound consists of three crystallographically unique Zn^II cations, two of which are located on special positions, one benzene-1,2,3-tricarboxylate anion, an OH^- anion (O7), a coordinated water molecule (O1W), and two disordered solvent water molecules (Fig. 1).

Atom Zn1 is located on an inversion center and is six coordinated by four oxygen atoms from four symmetry related 1,2,3-tricarboxybenzene anions and two symmetry related OH^- anions. The Zn1—O(carboxylate) distances are 2.022 (4) and 2.199 (3) Å. The Zn1—O7(OH^-) distance is 2.089 (3) Å. Atom Zn2, also located on a 2-fold axis, is four coordinated by two oxygen atoms from two symmetry related 1,2,3-tricarboxybenzene anions and two symmetry related OH^- anions. The Zn2—O (carboxylate) and Zn2—O7 distances are 1.943 (4) Å and 1.948 (3) Å, respectively. Atom Zn3, locate in a general position, is five coordinated by three oxygen atoms from three different 1,2,3-tricarboxybenzene anions, one OH^- anion and one water molecule (O1W). The Zn3—O(carboxylate) distances are 1.935 (4), 1.984 (3) and 2.008 (4) Å. The Zn3—O7 distance is 2.069 (4) Å, and the Zn3—O1W distance is 2.136 (5) Å. The Zn—O (carboxylate) distances are similar to those observed in related structures (Wu et al., 2009).

Each benzene-1,2,3-tricarboxylate anion bridges six Zn^II centers, and the OH^- anion bridges three Zn^II centers, leading to the formation of an infinite three-dimensional framework (Fig. 2). A series of O—H···O hydrogen bonds (Table 1) involving the tricarboxybenzene anions, the OH^- anion and the coordinating and two solvent water molecules (both of which are only partially occupied), further stabilize the crystal structure (Table 1).

Related literature

For complexes of benzene tricarboxylic acids, see: Chui et al. (1999); Majumder et al. (2005). For related structures, see: Wu et al. (2009).

S2. Experimental

A mixture of benzene-1,2,3-tricarboxylic acid (0.063 g, 0.3 mmol), NaOH (0.036 g, 0.9 mmol), and Zn(Ac)₂ (0.066 g, 0.3 mmol), in 10 ml H₂O was sealed in 18 ml Teflon-lined stainless steel container. The container was heated to 433 K and held at that temperature for 72 h. It was then cooled to room temperature at a rate of 10 K per hour and block-like colourless crystals of the title compound were isolated.

S3. Refinement

C-bound H-atoms were included in calculated positions and were refined as riding atoms: C—H = 0.93 Å, with U_iso = 1.2U_eq (C). The OH^- and water H atoms were located in difference Fourier maps and were refined with distance restraints of 0.86 (2) Å, or treated as riding atoms, all with U_iso(H) = 1.2U_eq(O). Water molecule O2W located on a 2-fold axis is 0.5 occupied, while water O3W is located in a general position is 0.25 occupied.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and Westrip (2010).

Figures

	Fig. 1. A view of the asymmetric unit of the title compound, showing the coordination environments of the three Zn^II centers and the 30% probability displacement ellipsoids [symmetry codes: (i) y + 1/4, -x + 1/4, z + 1/4; (ii) -y + 3/4, x - 1/4,- z + 3/4; (iii) -x + 1, -y, -z + 1; (iv) -x + 1, -y - 1/2, z; (v) -y + 3/4, x - 3/4, z + 1/4].
	Fig. 2. A view along the b axis of the three-dimensional structure of the title compound [the solvent water molecules and the H atoms have been omitted for clarity].

Poly[[aqua-µ₆-benzene-1,2,3-tricarboxylato-µ₃-hydroxido-dizinc] hemihydrate]

Crystal data

[Zn2(C9H3O6)(OH)(H2O)]·0.5H2O	Dx = 2.257 Mg m^−3
Mr = 381.89	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 2048 reflections
Hall symbol: -I 4ad	θ = 2.8–25.3°
a = 12.8412 (2) Å	µ = 4.31 mm^−1
c = 27.2647 (7) Å	T = 293 K
V = 4495.85 (15) Å^3	Block, colourless
Z = 16	0.28 × 0.23 × 0.21 mm
F(000) = 3024

Data collection

Oxford Diffraction Gemini R Ultra diffractometer	2048 independent reflections
Radiation source: fine-focus sealed tube	1402 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 10.0 pixels mm^-1	θmax = 25.3°, θmin = 2.8°
ω scan	h = −15→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −15→15
Tmin = 0.312, Tmax = 0.399	l = −22→32
9288 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0506P)^2] where P = (Fo^2 + 2Fc^2)/3
2048 reflections	(Δ/σ)max < 0.001
198 parameters	Δρmax = 0.80 e Å^−3
8 restraints	Δρmin = −0.53 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.5000	0.0000	0.5000	0.0208 (2)
Zn2	0.5000	−0.2500	0.49263 (3)	0.0250 (3)
Zn3	0.68168 (5)	−0.13663 (5)	0.57097 (2)	0.0274 (2)
O1	0.3829 (3)	−0.2239 (3)	0.44919 (13)	0.0350 (10)
O1W	0.8258 (4)	−0.1142 (4)	0.61415 (16)	0.0569 (13)
O2	0.4505 (3)	−0.0690 (3)	0.42997 (12)	0.0275 (9)
O3	0.3919 (3)	0.1070 (3)	0.36657 (11)	0.0224 (8)
O4	0.4706 (3)	0.0068 (3)	0.31306 (13)	0.0326 (10)
O5	0.2600 (3)	0.1066 (3)	0.28024 (12)	0.0312 (9)
O6	0.1945 (3)	−0.0076 (3)	0.22700 (13)	0.0411 (11)
O7	0.5375 (3)	−0.1373 (3)	0.53706 (12)	0.0209 (8)
C1	0.3132 (4)	−0.1383 (4)	0.38044 (18)	0.0250 (13)
C2	0.3150 (4)	−0.0597 (4)	0.34414 (17)	0.0201 (12)
C3	0.2429 (4)	−0.0677 (4)	0.30533 (19)	0.0273 (13)
C4	0.1747 (5)	−0.1498 (5)	0.3023 (2)	0.0485 (18)
H4	0.1296	−0.1543	0.2757	0.058*
C5	0.1720 (6)	−0.2254 (5)	0.3380 (3)	0.061 (2)
H5	0.1251	−0.2803	0.3357	0.074*
C6	0.2400 (5)	−0.2187 (5)	0.3774 (2)	0.0439 (17)
H6	0.2370	−0.2685	0.4022	0.053*
C7	0.3880 (4)	−0.1430 (4)	0.42282 (17)	0.0239 (12)
C8	0.3973 (4)	0.0242 (4)	0.34212 (17)	0.0197 (12)
C9	0.2329 (4)	0.0172 (4)	0.26799 (19)	0.0246 (12)
O2W	1.0000	−0.2500	0.5664 (4)	0.038 (3)	0.50
H2WA	0.9977	−0.2203	0.5475	0.057*	0.50
O3W	0.0743 (12)	−0.3649 (12)	0.2625 (5)	0.038 (4)	0.25
H3WA	0.0608	−0.3205	0.2396	0.057*	0.25
H3WB	0.0318	−0.4194	0.2582	0.057*	0.25
H1WA	0.885 (3)	−0.124 (5)	0.6006 (18)	0.057*
H1WB	0.825 (4)	−0.141 (5)	0.6431 (11)	0.057*
H7O	0.493 (3)	−0.139 (4)	0.5572 (14)	0.019 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0265 (5)	0.0185 (5)	0.0174 (4)	−0.0003 (4)	0.0020 (4)	0.0024 (3)
Zn2	0.0434 (6)	0.0173 (5)	0.0143 (4)	−0.0014 (4)	0.000	0.000
Zn3	0.0421 (5)	0.0242 (4)	0.0159 (3)	−0.0009 (3)	0.0057 (3)	0.0027 (3)
O1	0.047 (3)	0.030 (2)	0.028 (2)	−0.007 (2)	−0.0119 (19)	0.0136 (18)
O1W	0.054 (3)	0.073 (4)	0.043 (3)	0.000 (3)	−0.003 (2)	0.007 (3)
O2	0.040 (2)	0.028 (2)	0.0146 (18)	−0.0088 (19)	−0.0061 (16)	0.0001 (15)
O3	0.031 (2)	0.021 (2)	0.0149 (18)	−0.0029 (17)	−0.0013 (15)	0.0002 (15)
O4	0.036 (2)	0.037 (2)	0.024 (2)	−0.0105 (19)	0.0064 (18)	−0.0061 (17)
O5	0.047 (3)	0.024 (2)	0.0218 (19)	−0.0069 (19)	−0.0138 (18)	0.0090 (16)
O6	0.062 (3)	0.033 (2)	0.028 (2)	0.010 (2)	−0.025 (2)	−0.0059 (18)
O7	0.034 (2)	0.018 (2)	0.0101 (18)	−0.0017 (17)	0.0051 (17)	0.0005 (15)
C1	0.029 (3)	0.021 (3)	0.025 (3)	0.003 (3)	−0.006 (2)	0.000 (2)
C2	0.028 (3)	0.016 (3)	0.016 (3)	0.001 (2)	−0.002 (2)	−0.005 (2)
C3	0.033 (3)	0.021 (3)	0.028 (3)	0.002 (3)	−0.009 (3)	−0.002 (2)
C4	0.059 (5)	0.035 (4)	0.052 (4)	−0.009 (3)	−0.035 (4)	0.008 (3)
C5	0.065 (5)	0.041 (4)	0.078 (5)	−0.029 (4)	−0.037 (4)	0.020 (4)
C6	0.051 (4)	0.032 (4)	0.049 (4)	−0.009 (3)	−0.024 (3)	0.016 (3)
C7	0.025 (3)	0.033 (3)	0.013 (3)	0.005 (3)	0.003 (2)	0.000 (2)
C8	0.027 (3)	0.021 (3)	0.011 (2)	−0.001 (2)	−0.003 (2)	0.004 (2)
C9	0.023 (3)	0.026 (3)	0.025 (3)	0.001 (3)	−0.008 (2)	−0.001 (2)
O2W	0.039 (7)	0.030 (7)	0.044 (7)	−0.018 (5)	0.000	0.000
O3W	0.044 (11)	0.037 (10)	0.033 (9)	0.004 (8)	0.010 (8)	−0.014 (7)

Geometric parameters (Å, º)

Zn1—O5^i	2.022 (4)	O4—Zn3^vi	2.008 (4)
Zn1—O5^ii	2.022 (4)	O5—C9	1.245 (6)
Zn1—O7^iii	2.089 (3)	O5—Zn1^vii	2.022 (3)
Zn1—O7	2.089 (3)	O6—C9	1.263 (6)
Zn1—O2	2.199 (3)	O6—Zn3^viii	1.935 (4)
Zn1—O2^iii	2.199 (3)	O7—H7O	0.79 (2)
Zn2—O1^iv	1.943 (4)	C1—C6	1.399 (8)
Zn2—O1	1.943 (4)	C1—C2	1.413 (7)
Zn2—O7	1.948 (3)	C1—C7	1.504 (7)
Zn2—O7^iv	1.948 (3)	C2—C3	1.410 (7)
Zn3—O6^i	1.935 (4)	C2—C8	1.511 (7)
Zn3—O3^iii	1.984 (3)	C3—C4	1.373 (8)
Zn3—O4^v	2.008 (4)	C3—C9	1.497 (7)
Zn3—O7	2.069 (4)	C4—C5	1.374 (9)
Zn3—O1W	2.213 (5)	C4—H4	0.9300
O1—C7	1.265 (6)	C5—C6	1.388 (9)
O1W—H1WA	0.86 (2)	C5—H5	0.9300
O1W—H1WB	0.86 (2)	C6—H6	0.9300
O2—C7	1.259 (6)	O2W—H2WA	0.6405
O3—C8	1.257 (6)	O3W—H3WA	0.8614
O3—Zn3^iii	1.984 (3)	O3W—H3WB	0.8960
O4—C8	1.250 (6)
O5^i—Zn1—O5^ii	180.000 (1)	C8—O4—Zn3^vi	123.3 (3)
O5^i—Zn1—O7^iii	87.68 (15)	C9—O5—Zn1^vii	135.5 (3)
O5^ii—Zn1—O7^iii	92.32 (14)	C9—O6—Zn3^viii	133.0 (4)
O5^i—Zn1—O7	92.32 (14)	Zn2—O7—Zn3	120.15 (18)
O5^ii—Zn1—O7	87.68 (15)	Zn2—O7—Zn1	105.62 (15)
O7^iii—Zn1—O7	180.00 (15)	Zn3—O7—Zn1	114.77 (16)
O5^i—Zn1—O2	86.24 (15)	Zn2—O7—H7O	104 (4)
O5^ii—Zn1—O2	93.76 (15)	Zn3—O7—H7O	110 (4)
O7^iii—Zn1—O2	81.58 (13)	Zn1—O7—H7O	101 (4)
O7—Zn1—O2	98.42 (13)	C6—C1—C2	119.8 (5)
O5^i—Zn1—O2^iii	93.76 (15)	C6—C1—C7	116.4 (5)
O5^ii—Zn1—O2^iii	86.24 (15)	C2—C1—C7	123.8 (5)
O7^iii—Zn1—O2^iii	98.42 (13)	C3—C2—C1	117.6 (5)
O7—Zn1—O2^iii	81.58 (13)	C3—C2—C8	118.9 (4)
O2—Zn1—O2^iii	180.000 (1)	C1—C2—C8	123.1 (4)
O1^iv—Zn2—O1	104.9 (2)	C4—C3—C2	121.3 (5)
O1^iv—Zn2—O7	108.41 (15)	C4—C3—C9	117.7 (5)
O1—Zn2—O7	116.25 (16)	C2—C3—C9	120.9 (5)
O1^iv—Zn2—O7^iv	116.25 (16)	C3—C4—C5	121.1 (6)
O1—Zn2—O7^iv	108.41 (15)	C3—C4—H4	119.5
O7—Zn2—O7^iv	103.1 (2)	C5—C4—H4	119.5
O6^i—Zn3—O3^iii	135.77 (17)	C4—C5—C6	119.3 (6)
O6^i—Zn3—O4^v	102.75 (17)	C4—C5—H5	120.4
O3^iii—Zn3—O4^v	117.03 (14)	C6—C5—H5	120.4
O6^i—Zn3—O7	98.68 (14)	C5—C6—C1	120.9 (6)
O3^iii—Zn3—O7	87.62 (14)	C5—C6—H6	119.5
O4^v—Zn3—O7	107.46 (15)	C1—C6—H6	119.5
O6^i—Zn3—O1W	82.42 (17)	O2—C7—O1	124.3 (5)
O3^iii—Zn3—O1W	85.21 (16)	O2—C7—C1	119.8 (5)
O4^v—Zn3—O1W	81.20 (18)	O1—C7—C1	115.9 (5)
O7—Zn3—O1W	170.65 (17)	O4—C8—O3	122.0 (5)
C7—O1—Zn2	116.6 (3)	O4—C8—C2	115.0 (4)
Zn3—O1W—H1WA	120 (4)	O3—C8—C2	123.0 (5)
Zn3—O1W—H1WB	116 (4)	O5—C9—O6	125.4 (5)
H1WA—O1W—H1WB	110 (3)	O5—C9—C3	117.7 (4)
C7—O2—Zn1	128.5 (3)	O6—C9—C3	116.8 (5)
C8—O3—Zn3^iii	130.1 (3)	H3WA—O3W—H3WB	107.3
O1^iv—Zn2—O1—C7	−65.4 (4)	C7—C1—C2—C8	4.3 (8)
O7—Zn2—O1—C7	54.3 (4)	C1—C2—C3—C4	−1.2 (9)
O7^iv—Zn2—O1—C7	169.8 (4)	C8—C2—C3—C4	172.1 (6)
O5^i—Zn1—O2—C7	141.0 (4)	C1—C2—C3—C9	174.2 (5)
O5^ii—Zn1—O2—C7	−39.0 (4)	C8—C2—C3—C9	−12.5 (8)
O7^iii—Zn1—O2—C7	−130.8 (5)	C2—C3—C4—C5	2.2 (11)
O7—Zn1—O2—C7	49.2 (5)	C9—C3—C4—C5	−173.4 (7)
O2^iii—Zn1—O2—C7	−117 (100)	C3—C4—C5—C6	−0.5 (12)
O1^iv—Zn2—O7—Zn3	−45.2 (2)	C4—C5—C6—C1	−2.0 (12)
O1—Zn2—O7—Zn3	−163.02 (17)	C2—C1—C6—C5	2.9 (10)
O7^iv—Zn2—O7—Zn3	78.55 (17)	C7—C1—C6—C5	−175.8 (6)
O1^iv—Zn2—O7—Zn1	86.51 (19)	Zn1—O2—C7—O1	−39.5 (7)
O1—Zn2—O7—Zn1	−31.3 (2)	Zn1—O2—C7—C1	140.8 (4)
O7^iv—Zn2—O7—Zn1	−149.7 (2)	Zn2—O1—C7—O2	−15.6 (7)
O6^i—Zn3—O7—Zn2	91.9 (2)	Zn2—O1—C7—C1	164.2 (3)
O3^iii—Zn3—O7—Zn2	−132.1 (2)	C6—C1—C7—O2	−174.5 (5)
O4^v—Zn3—O7—Zn2	−14.5 (2)	C2—C1—C7—O2	6.8 (8)
O1W—Zn3—O7—Zn2	−172.0 (9)	C6—C1—C7—O1	5.7 (8)
O6^i—Zn3—O7—Zn1	−35.8 (2)	C2—C1—C7—O1	−172.9 (5)
O3^iii—Zn3—O7—Zn1	100.22 (18)	Zn3^vi—O4—C8—O3	27.5 (7)
O4^v—Zn3—O7—Zn1	−142.15 (16)	Zn3^vi—O4—C8—C2	−154.5 (3)
O1W—Zn3—O7—Zn1	60.3 (10)	Zn3^iii—O3—C8—O4	−156.6 (4)
O5^i—Zn1—O7—Zn2	−90.46 (18)	Zn3^iii—O3—C8—C2	25.5 (7)
O5^ii—Zn1—O7—Zn2	89.54 (18)	C3—C2—C8—O4	−75.5 (6)
O7^iii—Zn1—O7—Zn2	118.7 (5)	C1—C2—C8—O4	97.4 (6)
O2—Zn1—O7—Zn2	−3.92 (19)	C3—C2—C8—O3	102.5 (6)
O2^iii—Zn1—O7—Zn2	176.08 (19)	C1—C2—C8—O3	−84.5 (7)
O5^i—Zn1—O7—Zn3	44.24 (18)	Zn1^vii—O5—C9—O6	5.9 (9)
O5^ii—Zn1—O7—Zn3	−135.76 (18)	Zn1^vii—O5—C9—C3	−171.8 (4)
O7^iii—Zn1—O7—Zn3	−106.6 (3)	Zn3^viii—O6—C9—O5	−27.8 (9)
O2—Zn1—O7—Zn3	130.78 (17)	Zn3^viii—O6—C9—C3	149.8 (4)
O2^iii—Zn1—O7—Zn3	−49.22 (17)	C4—C3—C9—O5	151.0 (6)
C6—C1—C2—C3	−1.3 (8)	C2—C3—C9—O5	−24.6 (8)
C7—C1—C2—C3	177.3 (5)	C4—C3—C9—O6	−26.8 (8)
C6—C1—C2—C8	−174.3 (5)	C2—C3—C9—O6	157.6 (5)

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y+1/4, −x+1/4, z+1/4; (iii) −x+1, −y, −z+1; (iv) −x+1, −y−1/2, z; (v) −y+3/4, x−3/4, z+1/4; (vi) y+3/4, −x+3/4, z−1/4; (vii) −y+1/4, x−1/4, z−1/4; (viii) y+1/4, −x+3/4, −z+3/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2W	0.86 (2)	2.37 (4)	3.121 (7)	146 (6)
O1W—H1WB···O2^v	0.86 (2)	2.28 (5)	2.981 (6)	139 (6)
O1W—H1WB···O5^iii	0.86 (2)	2.40 (4)	3.084 (6)	137 (5)
O7—H7O···O3^ii	0.79 (2)	2.38 (2)	3.174 (5)	179 (5)
O2W—H2WA···O3W^i	0.64	2.30	2.776 (18)	134
O3W—H3WA···O2W^viii	0.86	1.94	2.776 (18)	164
O3W—H3WB···O4^ix	0.90	2.24	2.811 (15)	121

Symmetry codes: (i) −y+3/4, x−1/4, −z+3/4; (ii) y+1/4, −x+1/4, z+1/4; (iii) −x+1, −y, −z+1; (v) −y+3/4, x−3/4, z+1/4; (viii) y+1/4, −x+3/4, −z+3/4; (ix) −x+1/2, −y−1/2, −z+1/2.